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Author Jahng, Wan-Jin
Source CiteSeerX
Content type Text
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Subject Domain (in DDC) Computer science, information & general works ♦ Data processing & computer science
Subject Keyword Reaction Course ♦ A-bromovinyl Amino Acid ♦ Amino Protecting Group ♦ Alanine Racemase ♦ Halovinyl Amino Acid ♦ Plp-catalyzed Elimination ♦ Hydrogen Halide ♦ Tryptophan Synthase ♦ A-halovinyl Amino Acid ♦ Related Mechanism ♦ Fluorovinyl-gaba Analog ♦ A-branched Amino Acid ♦ Phenyselenyl Chloride ♦ Building Block ♦ Potential Inhibitor ♦ Synthetic Route ♦ Fficient Mechanism-based Inhibition ♦ Phenylselenyl Bromide ♦ Pyridoxal-dependent Enzyme ♦ Unnatural Peptide Synthesis ♦ Trojan Horse Inhibitor ♦ Internal Halovinyl Isomer ♦ Alkene Addition V ♦ Gaba Lransaminase ♦ Analogous Enzyme-bound ♦ N-trifluoroacetyl A-vinyl Amino Ester ♦ Amino Acid-processing Enzyme ♦ A-bromovinyl Amino Ester ♦ External Halovinyl Isomer ♦ Critical Determinant ♦ 5-exo-trig-like Cyclization ♦ 3-fluorovinylglycine Rr ♦ Reactive Allenic Intermediate ♦ Elsevier Science Ltd
Abstract Abstract: N-Trifluoroacetyl a-vinyl amino esters are smoothly converted to the corresponding a-chlorovinyl or a-bromovinyl amino esters through the agency of phenyselenyl chloride or phenylselenyl bromide, respectively, followed by oxidation and pyrolysis. Exclusively the (E)-external halovinyl isomer and the internal halovinyl isomer are observed. The amino protecting group is a critical determinant of the reaction course (alkene addition vs. 5-exo-trig-like cyclization). Copyright © 1996 Elsevier Science Ltd As part of a program directed at the synthesis of a-branched amino acids I as potential inhibitors of pyridoxal-dependent enzymes, and as building blocks for unnatural peptide synthesis, we sought a synthetic route to a-halovinyl amino acids. Early on, Abeles had postulated that halovinyl amino acids might serve as \"Trojan horse \" inhibitors for amino acid-processing enzymes via PLP-catalyzed elimination of the elements of hydrogen halide to yield a reactive allenic intermediate. 2 In fact, 3-chlorovinylglycine has been shown to produce fficient mechanism-based inhibition of alanine racemase. 3 3-Fluorovinylglycine rr versibly inhibits both alanine racemase 3 and tryptophan synthase. 4 Additionally, the internal T- and external T-(E)- and ~/-(Z)-fluorovinyl-GABA analogs inactivate GABA lransaminase by related mechanisms. 5 It follows that the higher halovinyl amino acids 6could in principle produce analogous enzyme-bound
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Education Level UG and PG ♦ Career/Technical Study
Learning Resource Type Article